Carbonic Acid Derivatives, Method for the Manufacture Thereof and the Use Thereof

Abstract

The invention relates to carboxylic acid derivatives which are obtained by reacting an unsaturated dicarboxylic acid anhydride (A) with a hydrophobic reactive component (B) that contains at least one group reacting to carboxylic acid anhydrides and has an average molecular weight of 200 to 50,000 Dalton. The inventive carboxylic acid derivatives are excellent as a substance for preventing efflorescences on surfaces of hardened cementitious construction materials and/or hydrophobizing the corresponding cementitious systems. Furthermore, said cementitious products absorb considerably smaller amounts of water as a result of the inventive additives such that frost damage and premature rusting of the reinforcing steel can be significantly reduced.

1 . Use of a carbonic acid derivative, which can be obtained by conversion of an unsaturated dicarbonic acid anhydride (A) with a hydrophobic reactive component (B), which has at least one group reactive with respect to a carbonic acid anhydride and which has a mean molecular weight of 200 to 50,000 Dalton, selected from the group of
 (B)(i) a polydimethyl siloxane of the general formula (I)   
     
       
         
         
             
             
         
       
       
         wherein 
         X=OH, NH 2 , SH, NHR 1 , 
         R 1 =H, CH 3 , C 2 H 5 , 
         m=1 to 50 and 
         n=1 to 6 
       
       or 
       (B)(ii) a polypropylene glycol of the general formulae (IIa) and/or (IIb) and/or (IIc) 
     
     
       
         
         
             
             
         
       
       
         wherein 
         a, b, c and d independent of one another mean 1 to 150 
       
       or 
       (B)(iii) a polyoxyalkylene anine of the general formulae (IIIa) and/or (IIIb) and/or (IIIc) 
     
     
       
         
         
             
             
         
       
       
         wherein 
         R 2 =H, CH 3 , 
         R 3 H, CH 3 , C 2 H 5 , and 
         x, y and z independent of one another mean 1 to 100 
       
       or 
       (B)(iv) a polyalkylene glycol based on alkylene diamines of the general formula (IV) 
     
     
       
         
         
             
             
         
       
       
         wherein 
         w=2 to 12, 
         r and s represent independent of one another 1 to 150 and 
         R 2  has the above-mentioned meaning 
       
       or 
       (B)(v) a triglyceride based on at least one hydroxy fatty acid, wherein the hydroxy fatty acid can be etherized 
       or 
       (B)(vi) an epoxy derivative produced by conversion of a di-, tri- or tetraglycidyl component (C)(i) with a possibly unsaturated reactive component (C)(ii), composed of a C 8 -C 28 -fatty acid, a C 8 -C 28 -Alcohol or a C 8 -C 28 -secondary amine for rendering cementitious products hydrophobic. 
     
   
   
       2 . Use as claimed in  claim 1 , characterized in that maleic acid anhydride or itacon acid anhydride is used as unsaturated dicarbonic acid anhydride. 
   
   
       3 . Use as claimed in  claim 1 , characterized in that the reactive component (B) has an average molecular weight of 500 to 10,000 Dalton. 
   
   
       4 . Use as claimed in  claim 1 , characterized in that m in formula (I) is 10 to 30. 
   
   
       5 . Use as claimed in  claim 1 , characterized in that the reactive component (B)(v) is consisting of a triglyceride derivative on the basis of hydroxy fatty acids, selected from the group of ricinoleic acid, cerebronic acid, nemotin acid or 12-hydroxy stearic acid. 
   
   
       6 . Use as claimed in  claim 1 , characterized in that glyceride compounds selected from the group of cyclohexane dimethanol diglycidylether, glycerine triglycidylether, neopentylglycol diglycidylether, pentaerythritol tetraglycidylether, 1,6-hexanediol diglycidylether, polypropylene glycol diglycidylether, polyethylene glycol diglycidylether, trimethylolpropane triglycidylether, bisphenol A diglycidylether, bisphenol F diglycidylether, 4,4-methylenebis (N,N-diglycidylaniline), tetraphenylolethane glycidylether, N,N-diglycidylaniline, diethyleneglycol diglycidylether, 1,4-butanediol diglycidylether or mixtures thereof are used as di-, tri- or tetraglycidyl compound (C)(i). 
   
   
       7 . Use as claimed in  claim 1 , characterized in that fatty acids from the group of tall oil fatty acid, stearic acid, palmitic acid, sunflower oil fatty acid, coconut oil fatty acid (C 8 -C 18 ), coconut oil fatty acid (C 12 -C 18 ), soy bean oil fatty acid, linseed oil fatty acid, dodecane acid, oleic acid, linoleic acid, palm kernel oil fatty acid, palm oil fatty acid, linolenic acid and/or arachidonic acid are used as reactive component (C)(ii). 
   
   
       8 . Use as claimed in  claim 1 , characterized in that alkanoles from the groups of 1-eicosanol, 1-octadecanol, 1-hexadecanol, 1-tetradecanol, 1-dodecanol, 1-decanol, 1-octanol are used as reactive component (C)(ii). 
   
   
       9 . Use as claimed in  claim 1 , characterized in that alkyl amines from the group of 2-ethylhexylamine, dipentylamine, dihexylamine, dioctylamine, bis(2-ethylhexyl)amine, N-methyloctadecylamine, didecylamine are used as reactive component (C)(ii). 
   
   
       10 . Use as claimed in  claim 1 , characterized in that the molar ratio of the unsaturated dicarbonic acid anhydride (A) with respect to the reactive component (B) is 0.1 to 1.0 mol (A) per mol of the reactive group of component (B). 
   
   
       11 . Use as claimed in  claim 1 , that the carbonic acid derivatives are used for suppressing efflorescences of hardened cementitious products. 
   
   
       12 . Use as claimed in  claim 1 , characterized in that the carbonic acid derivatives of the non-hardened cementitious products are added in a quantity of 0.01 to 5 wt % related to the cementitious portion. 
   
   
       13 . Carbonic acid derivatives, obtained by reacting an unsaturated dicarbonic acid anhydride (A) with a hydrophobic reactive component (B), which has at least one group reactive with respect to carbonic acid anhydrides and which has a mean molecular weight of 200 to 50,000 Dalton, selected from the group of
 (B)(ii) a polypropylene glycol of the general formulae (IIb) and/or (IIc)   
     
       
         
         
             
             
         
       
       
         wherein 
         a, b, c and d mean independent of one another 1 to 150 
       
       or 
       (B)(iii) a polyoxyalkylene amine of the general formulae (IIIa) and/or (IIIc) 
     
     
       
         
         
             
             
         
       
       
         wherein 
         R 2 =H, CH 3 , 
         R 3 =H, CH 3 , C 2 H 5 , and 
         x, y and z mean independent of one another 1 to 100 
       
       or 
       (B)(v) a triglyceride based on at least a hydroxy fatty acid, wherein the hydroxy fatty acid can be etherified by 1 to 100 mol of an ethylene oxide derivative 
       or 
       (B)(vi) an epoxy derivative, which was produced by reacting a di-, tri- or tetraglycidyl component (C)(i) with an optionally unsaturated reactive component (C)(ii) consisting of a C 8 -C 28 -fatty acid, a C 8 -C 28 -alcohol or a C 8 -C 28 -secondary amine. 
     
   
   
       14 . Carbonic acid derivatives as claimed in  claim 13 , characterized in that maleic acid anhydride, succinic acid anhydride or itacon acid anhydride is used as an unsaturated dicarbonic acid anhydride. 
   
   
       15 . Carbonic acid derivatives as claimed in  claim 13 , characterized in that the reactive component (B) has an average molecular weight of 500 to 10,000 Dalton. 
   
   
       16 . Carbonic acid derivatives as claimed in  claim 13 , characterized in that the reactive component (B)(v) is consisting of a triglyceride derivative on the basis of hydroxy fatty acids selected from the group of ricinoleic acid, cerebronic acid, nemotin acid or 12-hydroxy stearic acid. 
   
   
       17 . Carbonic acid derivatives as claimed in  claim 13 , characterized in that glycidyl compounds, selected from the group of cyclohexane dimethanol diglycidyl ether, glycerine triglycidyl ether, neopentylglycol diglycidylether, pentaerythritol tetraglycidylether, 1,6-hexanediol diglycidylether, polypropylene glycol diglycidylether, polyethylene glycol diglycidylether, trimethylol propane triglycidylether, bisphenol A diglycidylether, bisphenol F diglycidylether, 4,4-methylenebis (N,N-diglycidylaniline), tetraphenylolethane glycidylether, N,N-diglycidylanilinc, diethyleneglycol diglycidylether, 1,4-butanediol diglycidylether or mixtures thereof are used as di-, tri- or tetraglycidyl compound (C)(i). 
   
   
       18 . Carbonic acid derivatives as claimed in  claim 13 , characterized in that fatty acids of the group of tall oil fatty acid, stearic acid, palmitic acid, sunflower oil fatty acid, coconut oil fatty acid (C 8 -C 18 ), coconut oil fatty acid (C 2 -C 18 ), soy bean oil fatty acid, linseed oil fatty acid, dodecane acid, oleic acid, linoleic acid, palm kernel oil fatty acid, palm oil fatty acid, linolenic acid and/or arachidonic acid are used as reactive component (C)(ii). 
   
   
       19 . Carbonic acid derivative as claimed in  claim 13 , characterized in that alkanoles from the group of 1-eicosanol, 1-octadecanol, 1-hexadecanol, 1-tetradecanol, 1-dodecanol, 1-decanol, 1-octanol are used as reactive component (C)(ii). 
   
   
       20 . Carbonic acid derivatives as claimed in  claim 13 , characterized in that alkylamines of the group 2-ethylhexylamine, dipentylamine, dihexylamine, dioctylamine, bis(2-ethylhexyl)amine, N-methyloctadecylamine, didecylamine are used as reactive component (C)(ii). 
   
   
       21 . Carbonic acid derivates as claimed in  claim 13 , characterized in that the molar ratio of the unsaturated dicarbonic acid anhydride (A) to the reactive component (B) is 0.1. to 1.0 mol per mol of the reactive group of component (B). 
   
   
       22 . Method of manufacturing the carbonic acid derivatives as claimed in  claim 13 , characterized in that the unsaturated dicarbonic acid derivative (A) with the reactive component (B) is converted without the use of a solvent in a temperature range of 20 to 150° C. optionally in the presence of a catalyst. 
   
   
       23 . Method as claimed in  claim 22 , characterized in that an alkaline or alkaline earth salt of an organic acid such as sodium acetate or potassium acetate is used as a catalyst.